Composition comprising perfluoropolyether

ABSTRACT

A composition is disclosed which comprises an aryl perfluoropolyether, optionally a halogenated oil, and further optionally a thickening agent. The composition can be used as a lubricant itself or as an additive to an oil or grease lubricant and can withstand temperatures higher than 300° C. without decomposition. The halogenated oil can be a perfluoropolyether, a fluorosilicone, a polytrifluorochloroethylene, or combinations of two or more thereof. The thickening agent can be finely divided silica, boron nitride, clay, soap, poly(tetrafluoroethylene), clay, talc, silica, titanium dioxide, polydimethylsiloxane, polyurea, polyurethane, or combinations of two or more thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of and claims priority to U.S.application Ser. No. 11/218,259, filed Sep. 1, 2005, now U.S. Pat. No.7,838,475 allowed. The entire contents of both of the referencedapplications are hereby incorporated by reference.

FIELD OF THE INVENTION

The invention relates to compositions that can be used as lubricatingoils or as lubrication additives in oils or greases. The compositionscomprise mono-aryl and/or di-aryl substituted perfluoropolyetherfunctionalized materials.

BACKGROUND OF THE INVENTION

Trademarks and trade names used herein are shown in upper case.

Perfluoropolyether oils with exceptionally high thermal stability areuseful for extreme conditions. Greases are made by the addition ofthickening agents, for instance, finely divided silica, boron nitride,clay, soaps, or poly(tetrafluoroethylene) to oils. Both oils and greasestend to corrode metals at elevated temperatures, thus anticorrosionadditives are included. An example of such an anticorrosion additive isdisclosed in U.S. Pat. No. 6,184,187. The stability of thisphosphorus-containing anticorrosion additive has an upper temperaturelimit in service of about 180° C., whereas the perfluoropolyethers arestable at temperatures over 300° C. Though U.S. Pat. No. 6,653,511discloses perfluoropolyether primary bromides and iodides useful, forexample, to prepare lubricants, surfactants, and additives forlubricants and surfactants, development of more thermally stableanticorrosion additives that extend the use at higher temperatureswithout corrosion occurring is highly desirable.

SUMMARY OF THE INVENTION

The present invention provides a composition which comprises an arylperfluoropolyether which is a monofunctional aryl perfluoropolyether, adifunctional aryl perfluoropolyether, or combinations thereof.Optionally, the composition may further comprise one or both of ahalogenated oil and a thickening agent. The composition may also furthercomprise an additive. Typical additives are described below. Thecomposition may be used alone as a lubricant, or as a lubricantadditive, especially, as an anticorrosion additive to a lubricant.

DETAILED DESCRIPTION OF THE INVENTION

The composition of this invention may be said aryl perfluoropolyether orthe composition may comprise added components as described hereinbelow.The monofunctional perfluoropolyether of this invention has the formulaof R_(f)—(Y)_(a)—(C_(t)R_((u+v)))—(O—C_(t)R¹ _((u+v)))_(b)—R and thedifunctional perfluoropolyether of this invention has the formula ofR_(f) ¹—[(Y)_(a)—(C_(t)R_((u+v)))—(O—C_(t)R¹ _((u+v)))_(b)—R]₂

-   -   where    -   C_(t)R_((u+v)) is a divalent aryl group;    -   O—C_(t)R¹ _((u+v)) is a divalent aryl oxy group;    -   R_(f) is a polyether chain having a formula weight ranging from        about 400 to about 15,000 and comprises repeat units selected        from the group consisting of:    -   (a) J-O—(CF(CF₃)CF₂O)_(c)(CFXO)_(d)CFZ—,    -   (b) J¹-O—(CF₂CF₂O)_(e)(CF₂O)_(f)CFZ¹—,    -   (c) J²-O—(CF(CF₃)CF₂O)_(j)CF(CF₃)—,    -   (d) J³-O-(CQ₂-CF₂CF₂—O)_(k)-CQ₂-,    -   (e) J³-O—(CF(CF₃)CF₂O)_(g)(CF₂CF₂O)_(h)(CFX—O)_(i)—CFZ—,    -   (f) J⁴-O—(CF₂CF₂O)_(k′)—, and    -   (g) combinations of two or more thereof; and        -   where        -   the units with formulae CF₂CF₂O and CF₂O are randomly            distributed along the chain;        -   J is a fluoroalkyl group selected from the group consisting            of CF₃, C₂F₅, C₃F₇, CF₂Cl, C₂F₄Cl, C₃F₆Cl, and combinations            of two or more thereof;        -   c and d are numbers such that the c/d ratio ranges from            about 0.01 to about 0.5;        -   X is —F, —CF₃, or combinations thereof;        -   Z is —F, —Cl or —CF₃;        -   J¹ is a fluoroalkyl group selected from the group consisting            of —CF₃, —C₂F₅, —C₃F₇, —CF₂Cl, —C₂F₄Cl, and combinations of            two or more thereof;        -   e and f are numbers such that the e/f ratio ranges from            about 0.3 to about 5;        -   Z¹ is —F or —Cl,    -   J² is —C₂F₅, —C₃F₇, or combinations thereof;        -   j is an average number such that the formula weight of R_(f)            ranges from about 400 to about 15,000;        -   J³ is selected from the group consisting of —CF₃, —C₂F₅,            —C₃F₇, and combinations of two or more thereof;        -   k is an average number such that the formula weight of R_(f)            ranges from about 400 to about 15,000;    -   each Q is independently —F, —Cl, or —H;        -   g, h and i are numbers such that (g+h) ranges from about 1            to about 50, the i/(g+h) ratio ranges from about 0.1 to            about 0.5;    -   J⁴ is —CF₃, —C₂F₅, or combinations thereof;        -   k′ is an average number such that the formula weight of            R_(f) ranges from about 400 to about 15,000;    -   each R is independently —H, a halogen, —OH, —SO₃M, NR³ ₂, —NO₂,        —R⁴OH, —R⁴SO₃M, —R⁴NR³ ₂, —R⁴NO₂, —R⁴CN, —C(O)OR⁴, —C(O)OM,        —C(O)R⁴, or —C(O)NR³ ₂, or combinations of two or more thereof;        except that when b=0, R cannot be four hydrogen atoms and —OH,        or —Br, or —NH₂; or R cannot be solely H or —NO₂ or combinations        thereof;    -   each R¹ is independently H, —R⁴, —OR⁴, a halogen, —OH, —SO₃M,        —NR³ ₂, —NO₂, —CN, —R⁴OH, —R⁴SO₃M, —R⁴NR³ ₂, —R⁴NO₂, —R⁴CN,        —C(O)OR⁴, —C(O)OM, —C(O)R⁴, or C(O)NR³ ₂, or combinations of two        or more thereof;        -   each R³ is independently H, C₁-C₁₀ alkyl, or combinations of            two or more thereof;        -   R⁴ is a C₁-C₁₀ alkyl;        -   M is a hydrogen or metal ion (alkali metal, alkaline earth            metal, transition metal, or combinations of two or more            thereof) such as Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Cu,            Co, Zn, Ni, Fe, Ti, Zr, Va; preferably M is not aluminum;            more preferably M is H, Li, Na, K, Ca, or combinations of            two or more thereof;    -   a is 0 or 1;    -   b is 0-5;    -   Y is a linking divalent radical —CH₂OCH₂—, —(CH₂)_(o)—O—,        —(CF₂)_(n)—, —CF₂O—, —CF₂OCF₂—, —C(O)—, —C(S)—, or combinations        of two or more thereof;        -   n is about 1-5;        -   o is about 2-5;    -   t is equal to 6+u;    -   u is any combination of 0, 2, 4, 6, 8, 10, 12, 14, 16;    -   v is independently either 2 or 4;    -   Rf¹ is a divalent perfluoropolyether chain segment that can have        a number average formula weight of about 400 to about 15,000 and        can be selected from the group consisting of:    -   (i) —(CF₂CF₂O)_(e)(CF₂O)_(f)CF₂—,    -   (ii) —(C₃F₆O)_(p)(CF₂CF₂O)_(q)(CFXO)_(r)CF₂—,    -   (iii) —(CF₂CF₂O)(C₃F₆O)_(w)CF(CF₃)—,    -   (iv) —CF(CF₃)O(C₃F₆O)_(w)—Rf²—O—(C₃F₆O)_(w)CF(CF₃)—,    -   (v) -((CQ₂)CF₂CF₂O)_(s)CF₂CF₂—,        -   and combinations of two or more thereof; and        -   where        -   the units with formulae CF₂CF₂O and CF₂O can be randomly            distributed along the chain;        -   e, f, X, and Q are as defined above;        -   p, q and r are numbers such that (p±q) ranges from 1 to 50,            and the r/(p+q) ratio ranges from 0.1 to 0.05, and the            formula weight of R_(f) ¹ is from 400 to 15,000;        -   each w is independently 2 to 45;        -   Rf² is linear or branched —C_(m)F_(2m)—;            -   m is 1-10; and        -   s is an average number such that the formula weight of R_(f)            ¹ ranges from 400 to 15,000.

In the aryl perfluoropolyether of this invention, Y is preferably—(CF₂)_(n)—. Thus, the monofunctional perfluoropolyether preferably hasthe formula of R_(f)—(CF₂)_(n)—(C_(t)R_((u+v)))—(O—C_(t)R¹_((u+v)))_(b)—R and the difunctional perfluoropolyether preferably hasthe formula R_(f) ¹—[(CF₂)_(n)—(C_(t)R_((u+v)))—(O—C_(t)R¹_((u+v)))_(b)—R]₂, where R_(f), R_(f) ¹, n, t, R, R¹, u, v, and b are asdefined above.

Examples of aryl perfluoropolyethers useful in the composition of thisinvention when Y is —(CF₂)_(n)— include, but are not limited to

-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆Br₃H₂,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆F₃H₂,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄Cl,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄N(CH₃)₂,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₃[OC(O)CH₃]₂,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄SO₃M,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₃(OH)₂,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄OC₆H₅,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂(C₆H₄O)₂C₆H₅,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄OC₆H₄SO₃M,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂OC₆H₄OC₆H₄NO₂,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₁₀H₆SO₃M, or combinations of    two or more thereof where y is a number from about 3 to about 100.

Preferred examples of aryl perfluoropolyethers useful in the compositionof this invention include, but are not limited to

-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄SO₃M,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₃(OH)₂,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄OC₆H₅,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂(C₆H₄O)₂C₆H₅,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄OC₆H₄SO₃M,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂OC₆H₄OC₆H₄NO₂,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₁₀H₆SO₃M, or combinations of    two or more thereof where y is as defined above and M is H, Li, Na,    K, Ca, or combinations of two or more thereof.

Still, more preferred, examples of aryl perfluoropolyethers useful inthe composition of this invention include, but are not limited to:

-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄SO₃M,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄OC₆H₄SO₃M,-   CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₁₀H₆SO₃M, or combinations of    two or more thereof where y is as defined above and M is H, Li, Na,    K, Ca, or combinations of two or more thereof.

An aryl perfluoropolyether useful in the composition of this inventionis CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄SO₃M where y and M are asdefined above. Another aryl perfluoropolyether useful in the compositionof this invention is CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄OC₆H₄SO₃Mwhere y and M are as defined above. Still another arylperfluoropolyether useful in the composition of this invention isCF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₁₀H₆SO₃M where y and M are asdefined above.

The aryl perfluoropolyethers useful in the compositions of the inventioncan be produced by any means known to one skilled in the art such asthose disclosed in Journal of Organic Chemistry 1997, 62, pages7128-7136 and in U.S. Pat. No. 4,941,987, the disclosures of thesereferences are incorporated herein by reference.

For example, one process for producing an aryl perfluoropolyethercomprises contacting a perfluoropolyether primary halide such asperfluoropolyether iodide, optionally in the presence of a catalyticamount of a catalyst, with an aromatic compound to produce anaryl-substituted perfluoropolyether. An example of perfluoropolyetherprimary halide is a perfluoropolyether iodide, which is disclosed inU.S. Pat. No. 6,653,511, the disclosure of which is incorporated hereinby reference. Alternatively, the product of the reaction ofperfluoropolyether primary halide with an aromatic compound can befurther reacted to produce additional lubricating oils or additives.

Any compound that can promote the formation of a perfluoroalkyl orperfluoropolyether free radical can be used as catalyst. Cupric acetate,ferric acetate, ferric chloride, potassium hydroxide or combinations oftwo or more thereof is an example of suitable catalyst. Such catalystcan be present in the range of from about 0.0001 to about 5% of theprimary iodide compound by weight. The contacting can also be carriedout in the presence of an oxidizing agent such as, for example, hydrogenperoxide, butyl peroxide, ferrous chloride, benzoyl peroxide, potassiumpermanganate, or combinations of two or more thereof. A solvent can bepresent to solubilized the mixture and aid in the formation of arylperfluoropolyether products. Examples of solvents include acetone,acetic acid, formic acid, methanol, a mineral acid, or combinations oftwo or more thereof.

Any aromatic compound that can under go an aromatic substitution with aperfluoropolyether radical can be used as the aromatic compound.Examples of aromatic compounds include benzene, toluene, aniline,anisole, diacetoxybenezene, phenyl acetate, dimethoxybenzene, cresol,nitrophenol, diphenyl ether, phenol, diphenoxy benzene, or combinationsof two or more thereof.

The aryl perfluoropolyether can be, if desired, neutralized, sulfonated,nitrated or halogenated, for example, with an alkali metal hydroxide,alkali metal oxide, alkali metal salt, alkaline earth metal hydroxide,alkaline earth metal oxide, alkaline earth metal salt, sulfur trioxide,or halide. Specific preparations are provided in the Examples.

The reaction to prepare the aryl perfluoropolyether can be carried outat a temperature from about 30° C. to about 250° C. in a reaction vesselthat can contain the autogenous pressure sufficient to complete thereaction as determined by analysis, such as, for instance, up to about60 hours. The products can be recovered or purified by any means knownto one skilled in the art such as distillation, washing with a solventsuch as water or acetone or both, filtration, or distillation followingwashing to remove traces of water or solvent.

The composition of this invention comprising an aryl perfluoropolyethercan be used as a lubricant alone or as a lubricant additive. When usedas an additive, the composition may be mixed with an oil or grease, suchas a halogenated oil, or a grease to produce an oil or grease mixture,in an amount sufficient to provide a concentration of from 0.01 to 99%,or from about 0.1 to about 95%, or from 1 to 25% by weight, of the arylperfluoropolyether in the mixture. The composition comprising the arylperfluoropolyether disclosed herein can be readily mixed using any andany method providing adequate stirring suffices for preparing themixtures. The oil or grease can be any oil or grease known to oneskilled in the art, for example, any perfluoropolyethers orperfluoroalkyl ethers produced by E. I. du Pont de Nemours and Company,Wilmington, Del., USA (DuPont); by Ausimont, S.p.A., Milan, Italy; andby Daikin Industries, Ltd., Japan can be used.

The term “halogenated oil” used herein referred to a perfluoropolyether,a fluorosilicone, a polytrifluorochloroethylene, or combinations of twoor more thereof.

A common characteristic of perfluoropolyethers is the presence ofperfluoroalkyl ether moieties. Perfluoropolyether is synonymous toperfluoropolyalkylether. Other synonymous terms frequently used include“PFPE”, “PFPE oil”, “PFPE fluid”, and “PFPAE”.

For example, KRYTOX available from DuPont is a perfluoropolyether havingthe formula of CF₃—(CF₂)₂—O—[CF(CF₃)—CF₂—O]_(j′)—R′_(f). In the formula,j′ is 2-100, inclusive and R′_(f) is CF₂CF₃, a C₃ to C₆ perfluoroalkylgroup, or combinations thereof.

FOMBLIN and GALDEN fluids, available from Ausimont, Milan, Italy andproduced by perfluoroolefin photooxidation, can also be used. FOMBLIN-Ycan have the formula of CF₃O(CF₂CF(CF₃)—O—)_(m′)(CF₂—O—)_(n′)—R¹ _(f).Also suitable is CF₃O[CF₂CF(CF₃)O]_(m′)(CF₂CF₂O)_(o′)(CF₂O)_(n′)—R¹_(f). In the formulae R¹ _(f) is CF₃, C₂F₅, C₃F₇, or combinations of twoor more thereof; (m′+n′) is 8-45, inclusive; and m/n is 20-1000,inclusive; o′ is >1; (m′+n′+o′) is 8-45, inclusive; m′/n′ is 20-1000,inclusive.

FOMBLIN-Z can have the formula of CF₃O(CF₂CF₂—O—)_(p′)(CF₂—O)_(q′)CF₃where (p′+q′) is 40-180 and p′/q′ is 0.5-2, inclusive.

DEMNUM fluids, available from Daikin Industries, Japan, can also beused. It can be produced by sequential oligomerization and fluorinationof 2,2,3,3-tetrafluorooxetane, yielding the formula ofF—[(CF₂)₃—O]_(t′)—R² _(f) where R² _(f) is CF₃, C₂F₅, or combinationsthereof and t′ is 2-200, inclusive.

Perfluoropolyethers comprising branched or straight chain perfluoroalkylradical end groups, each of which having 3 or more carbon atoms per endgroup can also be used. Examples of such perfluoropolyethers can havethe formula of C_(r)F_((2r′+1))-A-C_(r)F_((2r′+1)) in which each r′ isindependently 3 to 6; A can be O—(CF(CF₃)CF₂—O)_(w′),O—(CF₂—O)_(x′)(CF₂CF₂—O)_(y′), O—(C₂F₄—O)_(w′),O—(C₂F₄—O)_(x′)(C₃F₆—O)_(y′), O—(CF(CF₃)CF₂—O)_(x′)(CF₂—O)_(y′),O—(CF₂CF₂CF₂—O)_(w′), O—(CF(CF₃)CF₂—O)_(x′)(CF₂CF₂—O)_(y′)—(CF₂—O)_(z′),or combinations of two or more thereof; preferably A isO—(CF(CF₃)CF₂—O)_(w′), O—(C₂F₄—O)_(w′), O—(C₂F₄—O)_(x′)(C₃F₆—O)_(y′),O—(CF₂CF₂CF₂—O)_(w′), or combinations of two or more thereof; w′ is 4 to100; x′ and y′ are each independently 1 to 100. Specific examplesinclude, but are not limited to, F(CF(CF₃)—CF₂—O)₉—CF₂CF₃,F(CF(CF₃)—CF₂—O)₉—CF(CF₃)₂, and combinations thereof. In such PFPEs, upto 30% of the halogen atoms can be halogens other than fluorine, suchas, for example, chlorine atoms.

Fluorosilicones suitable for use in the invention can be anyfluorocarbon containing silicone fluid. The preferred fluorosilicone isa fluorosilane, a fluorosiloxane, or combinations thereof. A suitablefluorosilicone can have the formula of R′_(f)—(CH₂)_(n″)—Si—R² ₃ inwhich R′_(f) can be the same as disclosed above, n″ can be 1 to 100, andeach R² can be independently an alkyl group, an alkoxy group, athioalkyl group, an amino group, an aryl group, or combinations of twoor more thereof. An example of suitable fluorosilicone is DOW CORNINGFS-1265 fluorosilicone oil from Dow Corning, Midland, Mich.

Polytrifluorochloroethylenes suitable for use in the invention can havethe formula of (—CCl₂CFCl—)_(s′) where s′ is 2-100, inclusive. Exampleof suitable polytrifluorochloroethylenes are HALOCARBON oils fromHalocarbon, Riveredge, N.J. The preferred polytrifluorochloroethylene isHALOCARBON 200.

The composition of this invention can also comprise a thickening agentto produce a grease. Thickening agents include, but are not limited to,polytetrafluoroethylene, talc, silica, clay, boron nitride, metal soaps,titanium dioxide, polydimethylsiloxane, polyurea, polyurethane orcombinations of two or more thereof. Minor amounts of other additivesuch as perfluoroalkyl surfactants or polyoxyperfluoroalkyl surfactants,or other additives known in the art (stabilizers, anticorrosive agents,anti-wear agents) may also be present in the composition of thisinvention. The thickening agent and/or additive can be present in thecomposition from about 0.01 to about 60%, or about 0.1 to about 20% byweight.

The upper limit can be determined by the National Lubricating GreaseInstitute (NLGI) grade specification requirement. Greases are gradedaccording to NLGI from 000 to 6 as measured by penetration (mm).Formulations for greases based on halogenated oils are well known to oneskilled in the art. For example, the aryl perfluoropolyether of thisinvention can be present in the grease in an amount of from about 0.01to about 90%, or about 0.1 to about 10%, by total weight of the greasecomposition.

An oil or grease comprising a composition of this invention can beproduced by any means known to one skilled in the art such as, forexample, mixing the components, that is, mixing a composition of thisinvention with an oil or grease or mixing a composition of thisinvention with an oil and a thickening agent, together. Since the meansare well known, the discussion is omitted herein in the interest ofbrevity.

The following methods and examples illustrate the invention.

Test Methods and Materials

Test Method 1. Heat Treatment of Mixtures of Perfluoropolyether and ArylPerfluoropolyether Compositions.

Two parts by weight of the perfluoropolyether derivative preparedaccording to the Examples were thoroughly mixed with 98 parts of KRYTOXGPL107-500 (a perfluoropolyether oil available from E. I. du Pont deNemours and Company). An aliquot was placed in a preheated oven at 200°C. for 24 hours. The sample was removed, allowed to cool, and subjectedto the pin corrosion test (Test Method 2). In each Example below, thecomposition was subjected to this heat treatment prior to evaluationusing the pin corrosion test.

Test Method 2. Pin Corrosion (Antirust) Test

The pin corrosion test (antirust test), fully detailed in U.S. Pat. No.6,184,187, incorporated herein by reference, was used. In summary,anti-rust properties of oil additives were tested using a variation ofASTM D-665, otherwise known as the “pin test”. The test used a C1018centerless ground cylindrical coupon [¼ inch diameter×2½ inch length(0.64 cm×6.4 cm), 1/16 inch slot (0.16 mm), P/N# 2200 from Metal SamplesCo., Munford Ala.). The coupon was cleaned and stored in toluene andthoroughly air dried (for 10 minutes) prior to use. The coupon wasplaced in the test fluid for 1 minute and excess fluid was allowed todrip off for 1 hour. It was then immersed in a beaker of medium hardwater, which was held at 80° C. for 24 hours with the use of aTEFLON-coated thermocouple and temperature controller. (The preparationof medium hard water is provided in U.S. Pat. No. 6,184,187). After the24-hour period, the pin was removed from the water, wiped gently toremove loose rust and evaluated. Evaluation was based on the following:

-   -   Excellent: No rust or light rust in a 24-hour period;    -   Good: Moderate rust occurring in a 24-hour period;    -   Fair: Severe rust occurring in a 24-hour period, but not        covering more than 35% of the surface.    -   Poor: Rust covering more than 35% of the surface.        Samples with the rating “fair” or better are considered        acceptable.        Test Method 3. Wear Test

Wear testing was conducted according to the America Society for Testingand materials (ASTM) Test D3233-93 (re-approved 1998), Standard TestMethods for Measurement of Extreme Pressure Properties of FluidLubricants (Falex Pin and Vee Block Methods).

CELITE 521 is a diatomaceous earth filter aid available from AldrichChemical, Milwaukee, Wis.

HFE-7100 is perfluorobutyl methyl ether available from 3M Company,Minneapolis, Minn.

KRYTOX (perfluoroalkylether; GPL (General Purpose Lubricants) 107-500 isa grade of KRYTOX) is available from DuPont.

KRYTOX Iodide [CF₃(CF₂)₂(OCF(CF₃)CF₂)_(z)OCF(CF₃)CF₂I where z is about8] is available from DuPont. It is produced by the methods described inU.S. Pat. No. 6,653,511, incorporated herein by reference.

ACRODISC syringe filters with PTFE membrane, 0.45 pin, are availablefrom VWR (West Chester, Pa.).

EXAMPLES

Gas chromatography/mass spectroscopy (GC/MS) was used to determinereaction completion and product characterization. Distillation undervacuum was conducted under 1 mm Hg (0.13 kPa).

Example 1 Preparation of KRYTOX BenzeneCF₃(CF₂)₂(OCF(CF₃)CF₂)_(z)OCF(CF₃)CF₂C₆H₅

KRYTOX Iodide (200 g; MW 1345) was placed in a 500-mL 4-neckround-bottom flask equipped with a mechanical stirrer, thermocouple anda reflux condenser. Glacial acetic acid (85 mL), 0.5 g of copper(II)acetate, and 55 g of benzene were added. The mixture was heated to 100°C. Benzoyl peroxide (160 g) was added in three increments over one and ahalf days. When analysis indicated all the iodide was reacted, the oilwas washed sequentially with water and acetone (100 mL each) and thendistilled under vacuum at 100° C. The resulting sample was then filteredin a Buchner funnel through a 0.25 inch (6.4 mm) layer of CELITE 521supported on a WHATMAN filter paper. Product (175 g) was retained.

Example 2 Preparation of KRYTOX Benzene Sulfonic AcidCF₃(CF₂)₂(OCF(CF₃)CF₂)_(z)OCF(CF₃)CF₂C₆H₄SO₃H

KRYTOX Benzene (100 g), prepared as in Example 1, was added to a 250-mL,4-neck round bottom flask equipped as in Example 1. Oleum (20%; 28 g)was dispensed into a dropping funnel and slowly dripped into the flaskover a 15 minute period. The flask contents were heated to 100° C. andstirred overnight. The flask was cooled to less than 30° C., and, whilecooling, water (about 100 mL) was slowly added, maintaining thetemperature at less than 30° C. This was followed by addition ofHFE-7100 (about 50 mL) and acetone (50 mL) to separate the oil. The oilwas washed three times with premixed acetone and water solution (100 mLeach) and distilled at 100° C. under vacuum. Product (82 g) wasretained.

Example 3 Preparation of Krytox DiacetoxybenzeneCF₃(CF₂)₂(OCF(CF₃)CF₂)_(z)OCF(CF₃)CF₂C₆H₃(OC(O)CH₃)₂

KRYTOX Iodide (526 g) and 108.2 g of diacetoxybenzene were added to a1-L round bottom flask. Glacial acetic acid (500 mL) and 0.5 g ofcopper(II) acetate were then added to flask. The reactants were heatedto 90° C. and benzoyl peroxide (75 g) was added in 5-g aliquots over a3-day period until the iodide had all reacted. The reaction product wascooled to room temperature. The mixture was washed twice with 500 mLmethanol to remove the non-fluorinated organic products. The solvent wasdistilled off at 90° C. under vacuum. The resulting sample was thenfiltered as in Example 1, to produce the product (506.65 g).

Example 4 Preparation of KRYTOX DihydroxybenzeneCF₃(CF₂)₂(OCF(CF₃)CF₂)_(z)OCF(CF₃)CF₂C₆H₃(OH)₂

KRYTOX diacetoxybenzene, prepared as in Example 3 (525 g) and HFE 7100(250 mL) were added to a 1-L round bottom flask. Potassium hydroxide (45g), water (250 mL) and methanol (250 mL) were added to the flask. Thereactants were heated to reflux at 60° C. After 4 hours of refluxing,10% hydrochloric acid (500 g) was added. The reaction mixture wasstirred until the KRYTOX diacetoxybenzene had reacted. The bottomproduct layer was separated and washed three times with equal volumes ofpremixed acetone and water (1:1). The product was distilled to 100° C.under vacuum and then filtered as in Example 1 to produce the product(465.30 g).

Example 5 Preparation of KRYTOX DimethoxybenzeneCF₃(CF₂)₂(OCF(CF₃)CF₂)_(z)OCF(CF₃)CF₂C₆H₃(OCH₃)₂

KRYTOX Iodide (100 g) and dimethoxybenzene (25.6 g) were added to a 1-Lround bottom flask equipped with a mechanical stirrer, thermocouple anda condenser. Glacial acetic acid (500 mL) and copper(II) acetate (1.0 g)were then added to flask. The reactants were heated to 90° C. Benzoylperoxide (75 g) was added in 5 g increments over a period of 6 days,until the iodide had all reacted as determined by analysis. After thereaction was complete, the mixture was washed twice with 250-mL ofmethanol. Perfluorohexane (50 mL) was added to assist in separations.The product was distilled to 100° C. under vacuum to produce finalproduct (85 g).

Example 6 Preparation of KRYTOX DihydroxybenzeneCF₃(CF₂)₂(OCF(CF₃)CF₂)_(z)OCF(CF₃)CF₂C₆H₃(OH)₂

Boron tribromide (18 g) was placed in a 250-mL 4-neck round-bottomedflask as described in Example 2. KRYTOX dimethoxybenzene (50 g),prepared as in Example 5 was dripped into the flask over a 15 minuteperiod. The mixture was stirred for 5 hours followed by the additionover 15 minutes, of about 50 g each of water, acetone andperfluorohexane. The oil layer was separated, filtered as in Example 1and then distilled to 100° C. under vacuum to produce 44 g of product.

Example 7 Preparation of Krytox Diphenyl EtherCF₃(CF₂)₂(OCF(CF₃)CF₂)_(z)OCF(CF₃)CF₂C₆H₄OC₆H₅

KRYTOX Iodide (150 g) was placed in a 500-mL 4-neck round-bottom flaskas described in Example 1. Glacial acetic acid (75 mL), copper(II)acetate (0.4 g), and diphenyl ether (85 g) were added. The mixture washeated to 100° C. followed by adding benzoyl peroxide (48 g). After 45minutes, more benzoyl peroxide (48 g) was added. Completion of thereaction within one day was indicated by consumption of the iodide asdetermined by analysis. When the reaction was complete, the oil waswashed sequentially with water and acetone (50 mL each), then distilledat 100° C. under vacuum, and then filtered as in Example 1 to producefinal product (130 g).

Example 8 Preparation of Krytox Nitrodiphenyl EtherCF₃(CF₂)₂(OCF(CF₃)CF₂)_(z)OCF(CF₃)CF₂C₆H₄OC₆H₄(NO₂)

100 mL HFE-7100 was added to a 4-neck round bottom flask equipped with amechanical stirrer, thermocouple and a condenser. To the flask, 25 g oftetramethylammonium nitrate and 50 g of trifluoromethanesulfonicanhydride were added to the flask. The mixture was allowed to stir atroom temperature for 1.5 hours. After stirring, 89 g of KRYTOX DiphenylEther, as prepared in Example 7, was dripped in using an additionfunnel. The mixture stirred and heated for 8 hours at 80° C. Once thereaction was done, 100 mL of water was slowly added. The oil wasseparated with HFE 7100 and acetone. The product was then isolated,washed several times with acetone and water, distilled with an oil pumpvacuum at 100° C., and filtered through celite and Whatman #1 filterpaper. 79.8 g of product was retained.

Example 9 Preparation of Krytox Diphenoxy BenzeneCF₃(CF₂)₂(OCF(CF₃)CF₂)_(z)OCF(CF₃)CF₂(C₆H₄O)₂C₆H₅

KRYTOX Iodide (50 g) was added to a 250-mL, 4-neck round-bottom flaskdescribed in Example 2. To the flask, glacial acetic acid (50 mL),copper(II) acetate (0.13 g), and diphenoxy benzene (70 g) were added.The contents were stirred and heated to 90° C. Then, three portions ofbenzoyl peroxide (17 g each, total 51 g) were added at 45 minute,intervals. The mixture was stirred at 90° C. for two days. Completion ofthe reaction was confirmed by analysis. The oil was separated with HFE7100 as described in Example 2. The product layer was then isolated,washed three times with water and acetone (50 mL each), distilled undervacuum at 100° C. and then filtered as described in Example 1 to produceproduct (35 g).

Example 10 KRYTOX Diphenyl Ether Sulfonic AcidCF₃(CF₂)₂(OCF(CF₃)CF₂)_(z)OCF(CF₃)CF₂OC₆H₄OC₆H₄SO₃H

KRYTOX diphenyl ether (78 g, prepared as in Example 7) was added to a250-mL, 4-neck round-bottom flask described in Example 2, followed bydripping into the flask over a 15-minute period 20% oleum (28 g) througha dropping funnel. The flask contents were heated to 100° C. and stirredovernight. With cooling as in Example 2, water (100 mL) was slowlyadded. HFE-7100 (50 mL) and acetone (50 mL) were added to separate theoil. The oil was then isolated, washed three times with acetone andthree times with water (50 mL each washing) and distilled at 100° C.under vacuum to produce viscous product (69.5 g).

Example 11 Preparation of Krytox Benzene Sulfonic Acid Ca Salt(CF₃(CF₂)₂(OCF(CF₃)CF₂)_(z)OCF(CF₃)CF₂C₆H₄SO₃)₂Ca

KRYTOX benzene sulfonic acid (50 g, prepared as in Example 3) was placedin a 250-mL round-bottom flask as described in Example 2. Calciumacetate (6 g) dissolved in water (60 mL) and HFE 7100 (50 mL) were addedto the flask. The contents were stirred and refluxed at 60° C. After 24hours of reflux and stirring, the product was distilled under vacuum at100° C. to produce viscous product (49 g).

Example 12 Preparation of 2% KRYTOX Benzene Sulfonic Acid Ca Salt in GPL107-500

GPL 107-500 (98 g) was placed in a 250-mL round-bottom flask asdescribed in Example 2. KRYTOX benzene sulfonic acid (2 g, prepared asin Example 2) and calcium oxide (0.08 g) were added to the flask. Themixture was heated to 200° C. and stirred for 24 hours. The mixture wasfiltered through a 0.45 μm poly(tetrafluoroethylene) syringe filter toproduce oil product (90 g).

Example 13 Preparation of Krytox Benzene Sulfonic Acid Li SaltCF₃(CF₂)₂(OCF(CF₃)CF₂)_(z)OCF(CF₃)CF₂C₆H₄SO₃Li

KRYTOX benzene sulfonic acid (50 g, prepared as in Example 2) was placedin a 250-mL round-bottom flask as described in Example 2. Lithiumacetate (3.6 g) and HFE 7100 (50 mL) were added to the flask. Thecontents were stirred and refluxed at 60° C. for 24 hours followed bydistillation under vacuum at 100° C. to produce viscous product (45 g).

Example 14 Preparation of 2% KRYTOX Benzene Sulfonic Acid Li Salt in GPL107-500

GPL 107-500 (98 g) was placed in a 250-mL round-bottom flask equipped asdescribed in Example 2. KRYTOX benzene sulfonic acid (2 g, prepared asin Example 2) and lithium acetate dihydrate (0.15 g) were added. Themixture was heated to 200° C. and stirred for 24 hours, followed byfiltration through WHATMAN #1 filter paper to produce an oil product(90.8 g).

Example 15 Preparation of KRYTOX Benzene Sulfonic Acid Na SaltCF₃(CF₂)₂(OCF(CF₃)CF₂)_(z)OCF(CF₃)CF₂C₆H₄SO₃Na

KRYTOX benzene sulfonic acid (50 g, prepared as in Example 2) was placedin a 250-mL round-bottom flask as described in Example 2. Sodium acetate(2.9 g) and HFE 7100 (50 mL) were added and the contents were stirredand refluxed at 60° C. for 48 hours. The product was filtered asdescribed in Example 12 (syringe filter) and then distilled under vacuumto 100° C. to produce final product (36 g).

Example 16 Preparation of 2% KRYTOX Benzene Sulfonic Acid Na Salt in GPL107-500

GPL 107-500 (98 g) was placed in a 250-mL round-bottom flask asdescribed for Example 2. KRYTOX benzene sulfonic acid (2 g, prepared asin Example 2) and sodium acetate (0.2 g) were added. The mixture washeated to 200° C. and stirred for 24 hours, followed by filtrationthrough WHATMAN #1 paper to produce an oil product (91.6 g).

Example 17 Preparation of 2% KRYTOX Benzene Sulfonic Acid Ni Salt in GPL107-500

GPL 107-500 (98 g) was placed in a 250-mL round-bottom flask asdescribed in Example 2. KRYTOX benzene sulfonic acid (2 g, prepared asin Example 2) and nickel acetate tetrahydrate (0.36 g) were added to theflask. The mixture was heated to 200° C. and stirred for 24 hours,followed by filtration as described in Example 12 (syringe filter) toproduce an oil product (90.2 g).

Example 18 Preparation of 2% KRYTOX Benzene Sulfonic Acid Fe Salt in GPL107-500

The process was the same as described in Example 12 except that calciumoxide (0.08 g) was replaced with iron acetate (0.25 g). The reaction washeated for 24 hours at 200° C.; no filtration was needed to produce anoil product (93.5 g).

Comparative Example A

A sample was prepared according to the procedure of Example 3 in U.S.Pat. No. 6,184,187.

Tests Results.

The above-described products were tested, after the heat treatment ofTest Method 1, using the Pin Corrosion Test (Test Method 2). Wear testswere conducted according to Test Method 3. The Load to Failure (Pin onV-Block) Test was run according to ASTM D-3233. The results are shown inTable 1 below. The conditions for wear test: 5% compound in KRYTOX GPL106.

TABLE 1 Pin on V-Block Pin Test Result Pin on V-Block TorqueCompound^(a) (200° C., 24 hr) Load lb (kg) in-lbf (N-m) KRYTOX Excellent3000 (1361) 71.9 (82.1) Benzene Sulfonic Acid KRYTOX Fair N/T^(b) N/TDiphenyl Ether KRYTOX Excellent N/T N/T Nitrodiphenyl Ether KRYTOXDiphenyl Excellent N/T N/T Ether Sulfonic Acid KRYTOX Diphenoxy Good N/TN/T Benzene KRYTOX Dihydroxy Excellent 3000 (1316)^(c) 86.6 (97.8)^(c)Benzene KRYTOX benzene Excellent 3000 (1316) 63.0 (71.2) sulfonic acidCa Salt KRYTOX benzene Excellent N/T N/T sulfonic acid Li Salt KRYTOXbenzene Excellent N/T N/T sulfonic acid Na Salt KRYTOX benzene ExcellentN/T N/T sulfonic acid Ni Salt KRYTOX benzene Excellent N/T N/T sulfonicacid Fe Salt Comparative Poor N/T N/T Example A Control (GPL 107)^(d)Poor N/T N/T Control (GPL 106)^(d) Poor 3000 (1361), 87.0 (98.3), 3000(1361)^(c) 92.7 (104.7)^(c) ^(a)Chemical compositions are shown in theindividual examples. ^(b)N/T = not tested ^(c)Second series tested.^(d)KRYTOX perfluoroalkylether.

The results show improved performance of the formulations comprising acomposition the invention comprising an aryl perfluoropolyether, asanticorrosion additive, and with performance in the wear test comparableto control tests.

1. A composition comprising an aryl perfluoropolyether which is amonofunctional aryl perfluoropolyether having the formula ofR_(f)—(Y)_(a)—(C_(t)R_((u+v)))—(O—C_(t)R¹ _((u+v)))_(b)—R wherein R_(f)has a formula weight of about 400 to about 15,000; R_(f) comprisesrepeat units selected from the group consisting of (a)J-O—(CF(CF₃)CF₂O)_(c)(CFXO)_(d)CFZ—, (b)J¹-O—(CF₂CF₂O)_(e)(CF₂O)_(f)CFZ¹—, (c) J²-O—(CF(CF₃)CF₂O)_(j)CF(CF₃)—,(d) J³-O-(CQ₂-CF₂CF₂—O)_(k)-CQ₂-, (e)J³-O—(CF(CF₃)CF₂O)_(g)(CF₂CF₂O)_(h)(CFX—O)_(i)—CFZ—, (f)J⁴-O—(CF₂CF₂O)_(k)—CF₂—, and (g) combinations of two or more thereof;and where the units with formulae CF₃CF₂O and CF₂O are randomlydistributed along the chain; J is CF₃, C₂F₅, C₃F₇, CF₂Cl, C₂F₄Cl,C₃F₆Cl, or combinations of two or more thereof; c and d are numbers suchthat the c/d ratio ranges from about 0.01 to about 0.5; X is —F, —CF₃,or combinations thereof; Z is —F, —Cl or —CF₃; Z¹ is —F or —Cl, J¹ isCF₃, C₂F₅, C₃F₇, CF₂Cl, C₂F₄Cl, or combinations of two or more thereof;e and f are numbers such that the elf ratio ranges from about 0.3 toabout 5; J² is —C₂F₅, —C₃F₇, or combinations thereof; j is an averagenumber such that the formula weight of R_(f) ranges from about 400 toabout 15,000; J³ is CF₃, C₂F₅, C₃F₇, or combinations of two or morethereof; k is an average number such that the formula weight of R_(f)ranges from about 400 to about 15,000; each Q is independently —F, —Cl,or —H; g, h and i are numbers such that (g+h) ranges from about 1 toabout 50, the i/(g+h) ratio ranges from about 0.1 to about 0.5; J⁴ isCF₃, C₂F₅, or combinations thereof; k′ is an average number such thatthe formula weight of R_(f) ranges from about 400 to about 15,000; eachR is independently —H, a halogen, —OH, —SO₃M, NR³ ₂, —NO₂, —R⁴OH,—R⁴SO₃M, —R⁴NR³ ₂, —R⁴NO₂, —R⁴CN, —C(O)OR⁴, —C(O)OM, —C(O)R⁴, —C(O)NR³₂, or combinations of two or more thereof; except that when b=0, Rcannot be four hydrogen atoms and —OH, or —Br, or —NH₂; or R cannot besolely H or —NO₂, or combinations thereof; each R¹ is independently H,—R⁴, —OR⁴, a halogen, —OH, —SO₃M, —NR³ ₂, —NO₂, —CN, —R⁴OH, —R⁴SO₃M,—R⁴NR³ ₂, —R⁴NO₂, —R⁴CN, —C(O)OR⁴, —C(O)OM, —C(O)R⁴, —C(O)NR³ ₂, orcombinations of two or more thereof provided that if b=0, thecombination of R and R² cannot be four or more hydrogen atoms and —OH,—Br, —NH₂, or —NO₂; each R³ is independently H, C₁-C₁₀ alkyl, orcombinations of two or more thereof; R⁴ is a C₁-C₁₀ alkyl; M is ahydrogen or metal ion; a is 0 or 1; b is 0-5; Y is a divalent radical—CH₂OCH₂—, —(CH₂)_(o)—O—, —(CF₂)_(n)—, —CF₂O—, —CF₂OCF₂—, —C(O)—,—C(S)—, or combinations of two or more thereof; n is about 1 to about 5;o is about 2 to about 5; t is equal to 6+u; u is any combination of 0,2, 4, 6, 8, 10, 12, 14, 16; and v is independently either 2 or
 4. 2. Acomposition according to claim 1 wherein M is H, Li, Na, K, Ca, orcombinations of two or more thereof.
 3. A composition according to claim1 wherein b is 0 and R is not four hydrogen atoms and —OH, or —Br, or—NH₂; or solely H or —NO₂ groups or combinations thereof.
 4. Acomposition according to claim 1 wherein said aryl perfluoropolyether isCF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆Br₃H₂,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆F₃H₂,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄Cl,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄N(CH₃)₂,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₃[OC(O)CH₃]₂,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄SO₃M,CF₃(CF₂)₂(OCF(CF₂)_(y)OCF(CF₃)CF₂C₆H₃(OH)₂,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄OC₆H₅,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂(C₆H₄O)₂C₆H₅,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄OC₆H₄SO₃M,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂OC₆H₄OC₆H₄NO₂,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₁₀H₆SO₃M, or combinations of twoor more thereof and y is from about 3 to about
 100. 5. A compositionaccording to claim 4 wherein said aryl perfluoropolyether isCF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄SO₃M,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₃(OH)₂,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄OC₆H₅,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂(C₆H₄O)₂C₆H₅,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄OC₆H₄SO₃M,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂OC₆H₄OC₆H₄NO₂,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₁₀H₆SO₃M, or combinations of twoor more thereof.
 6. A composition according to claim 5 wherein said arylperfluoropolyether is CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄SO₃M,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄OC₆H₄SO₃M,CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₁₀H₆SO₃M, or combinations of twoor more thereof and M is H, Li, Na, K, Ca, or combinations of two ormore thereof.
 7. A composition according to claim 6 wherein said arylperfluoropolyether is CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄SO₃M. 8.A composition according to claim 6 wherein said aryl perfluoropolyetheris CF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₆H₄OC₆H₄SO₃M.
 9. A compositionaccording to claim 6 wherein said aryl perfluoropolyether isCF₃(CF₂)₂(OCF(CF₃)CF₂)_(y)OCF(CF₃)CF₂C₁₀H₆SO₃M.
 10. A compositionaccording to claim 1 wherein said composition is said arylperfluoropolyether.
 11. A composition according to claim 7 wherein saidcomposition is said aryl perfluoropolyether.
 12. A composition accordingto claim 8 wherein said composition is said aryl perfluoropolyether. 13.A composition according to claim 9 wherein said composition is said arylperfluoropolyether.
 14. A composition according to claim 1 or 4, furthercomprising a halogenated oil which is a perfluoropolyether.
 15. Acomposition according to claim 14 wherein said aryl perfluoropolyetheris present in said composition from about 0.01 to about 99% by weight.16. A composition according to claim 1 or 4, further comprising ahalogenated oil and a thickening agent, wherein said halogenated oil isa perfluoropolyether, a fluorosilicone, a polytrifluorochloroethylene,or combinations of two or more thereof; and said thickening agent ispolytetrafluoroethylene, talc, silica, clay, boron nitride, metal soaps,titanium dioxide, polydimethylsiloxane, polyurea, polyurethane, orcombinations of two or more thereof.
 17. A composition according toclaim 16 further comprising an additive wherein said additive isperfluoroalkyl surfactant, polyoxyperfluoroalkyl surfactant, oil orgrease stabilizer, anticorrosive agent, anti-wear agent, or combinationsof two or more thereof.
 18. A composition according to claim 17 whereinsaid aryl perfluoropolyether is present in said composition from about0.1 to about 90% and said thickening agent is present in saidcomposition from about 0.01 to about 60%, both by weight.
 19. A greasecomposition comprising, or produced by combining, a halogenated oil, anaryl perfluoropolyether and a thickening agent, wherein said halogenatedoil is a perfluoropolyether, a fluorosilicone,polytrifluorochloroethylene, or combinations of two or more thereof;said aryl perfluoropolyether is the same as recited in claim 1 or 4, andsaid thickening agent is polytetrafluoroethylene, talc, silica, clay,boron nitride, metal soaps, titanium dioxide, polydimethylsiloxane,polyurea, polyurethane, or combinations of two or more thereof.
 20. Agrease composition according to claim 19 further comprising an additivewherein said additive is perfluoroalkyl surfactant,polyoxyperfluoroalkyl surfactant, oil or grease stabilizer,anticorrosive agent, anti-wear agent, or combinations of two or morethereof.
 21. A grease composition according to claim 20 wherein saidaryl perfluoropolyether is present from about 0.1 to about 90% and saidthickening agent is present from about 0.01 to about 50%, both by weightof said grease.
 22. A composition comprising, or produced by combining,a perfluoropolyether, an aryl perfluoropolyether and a thickening agent,wherein said aryl perfluoropolyether is the same as recited in claim 5;and said thickening agent is polytetrafluoroethylene, talc, silica, day,boron nitride, metal soaps, titanium dioxide, polydimethylsiloxane,polyurea, polyurethane, or combinations of two or more thereof.